CN105906659A - Dimethyldichlorosilance purification process and system - Google Patents
Dimethyldichlorosilance purification process and system Download PDFInfo
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- CN105906659A CN105906659A CN201610301102.6A CN201610301102A CN105906659A CN 105906659 A CN105906659 A CN 105906659A CN 201610301102 A CN201610301102 A CN 201610301102A CN 105906659 A CN105906659 A CN 105906659A
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- 238000000746 purification Methods 0.000 title claims abstract description 14
- 239000000047 product Substances 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 239000012043 crude product Substances 0.000 claims abstract description 19
- 239000000126 substance Substances 0.000 claims abstract description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000013067 intermediate product Substances 0.000 claims abstract description 14
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 3
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 29
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 24
- 238000009835 boiling Methods 0.000 claims description 23
- 238000007599 discharging Methods 0.000 claims description 17
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 16
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 238000003860 storage Methods 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000005046 Chlorosilane Substances 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 8
- 229910000077 silane Inorganic materials 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 229910052763 palladium Inorganic materials 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 5
- -1 De-low tower Chemical compound 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 3
- 239000007792 gaseous phase Substances 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 2
- VVSSBZADJNQFMD-UHFFFAOYSA-N dichloro(dimethyl)silane silane Chemical compound [SiH4].C[Si](C)(Cl)Cl VVSSBZADJNQFMD-UHFFFAOYSA-N 0.000 claims description 2
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 claims description 2
- 238000001802 infusion Methods 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 239000012535 impurity Substances 0.000 abstract description 12
- 239000000203 mixture Substances 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 229910052710 silicon Inorganic materials 0.000 abstract description 2
- 239000010703 silicon Substances 0.000 abstract description 2
- 239000000178 monomer Substances 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 6
- PFMKUUJQLUQKHT-UHFFFAOYSA-N dichloro(ethyl)silicon Chemical compound CC[Si](Cl)Cl PFMKUUJQLUQKHT-UHFFFAOYSA-N 0.000 description 6
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical compound C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 229920002379 silicone rubber Polymers 0.000 description 4
- 239000004945 silicone rubber Substances 0.000 description 4
- ZOYFEXPFPVDYIS-UHFFFAOYSA-N trichloro(ethyl)silane Chemical compound CC[Si](Cl)(Cl)Cl ZOYFEXPFPVDYIS-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- POFAUXBEMGMSAV-UHFFFAOYSA-N [Si].[Cl] Chemical compound [Si].[Cl] POFAUXBEMGMSAV-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/12—Organo silicon halides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/20—Purification, separation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
The invention discloses a dimethyldichlorosilance purification process and system, and belongs to the technical field of organic silicon production. The purification process comprises the following steps of (1) passing a dimethyldichlorosilance coarse product through a low-boiling-point substance removing tower to remove low-boiling-point substances, and obtaining a first intermediate product; (2) introducing the first intermediate product into a high-boiling-point substance removing tower, mixing tower top gas phase with chlorine hydride gas, then introducing the mixture into a fixed bed reactor; under the effect of a catalyst, converting hydrosilane in a crude product into corresponding chlorsilane to obtain a second intermediate product; (3) passing the second intermediate product through a high-boiling-point substance removing upper tower, and removing the chlorsilane to obtain the product. The purification system comprises the low-boiling-point substance removing tower, the high-boiling-point substance removing lower tower, the fixed bed reactor and the high-boiling-point substance removing upper tower. By using the technical scheme, the purification of dimethyldichlorosilance can reach 99.98 percent or above; the removal rate of impurities reaches 99.9 percent or above.
Description
Technical field
The present invention relates to technical field of organic silicon production, particularly relate to purifying technique and the system of a kind of dimethyldichlorosilane.
Background technology
It is known that the various types of materials of organosilicon is by " direct method " synthesis technique target product (CH3)2SiCl2For raw material,
It is transformed into the siloxane polymer with various different functional groups and structure by poly-condensation and hydrolysis, is further processed into all kinds of
Product.When especially preparing silicone rubber when preparing silicone oil, silicone rubber, it is desirable to monomer (CH used3)2SiCl2There is the highest purity,
I.e. more than 99.98%.
The component of the methylchlorosilane mix monomer that " direct method " synthesizes is many, and boiling-point difference is away from little, and there is azeotropic, separation requirement
The highest, therefore monomer is isolated and purified extremely difficult.Dimethyldichlorosilane ((CH3)2SiCl2, boiling point 70.2 DEG C) with close thereafter
Key component ethyl dichlorosilane (CH3CH2SiHCl2, boiling point 74.0 DEG C) boiling point differ only 3.8 DEG C, rectification require higher.
EtSiHCl2Content content in mix monomer is extremely low, and differs very with high-boiling components (boiling point mixture higher than 70 DEG C) boiling point
Far, it is being difficult to carry removing secretly except height boiling link.When preparing silicone rubber, if the impurity trifunctional amount comprised is more than 0.05%,
Cannot obtain high molecular chain polymer, can only obtain the polymer of three-dimensional structure, this polymer with cross-linked structure exists
Be not easy during kneading with uniform filling mix, therefore can severely impact the heat stability of silicone rubber, electric insulation, mechanical strength
Etc. performance.So siloxane polymer important quality feature is containing the most a small amount of trifunctional in its polymeric skeleton
Impurity.
Industrially meet the purity (CH more than 99.98% needed for special purpose to obtain to have3)2SiCl2Monomer, all uses
Precision fractionation method, and use the efficient fractionating column of about 200 pieces theoretical cam curves, pay the biggest energy penalty, rectification simultaneously
The steam energy consumption of device accounts for more than the 70% of total steam consumption.
Silicone industry in China manufacturer rectification gained (CH at present3)2SiCl2Product is compared with Foreign Advanced Lerel, and purity is the highest, and
Steam consumption is relatively big, causes product competitiveness low, it is therefore necessary to rectification working process carries out relation technological researching to reach to improve
Product purity and the purpose of reduction energy consumption.
The method separating methylchlorosilane mix monomer of document introduction at present has Physical and chemical method, mainly includes one
As rectification method, extraction and fraction, fractionation and catalysis impurity removal method etc..
Catalysis impurity removal method is simple to operate, easily realizes continuous operation, can effectively reduce the energy consumption thing of follow-up methylchlorosilane rectification
Consumption.Silicone industry in foreign countries enterprise report has employing catalytic reaction method to be removed by ethyl dichlorosilane.Detailed process is at fixed bed reaction
In device, take the catalyst using hydrogen chloride gas and Pd, Pt, Rh, Ru, Ni, Os, Ir and compound thereof by hydrogeneous alkane
Base silane impurity is transformed into corresponding alkylchlorosilane, and the boiling point difference between target product and impurity can be made by this method to increase,
To reduce follow-up chlorosilane rectification difficulty.But this method requires hydrogen chloride excess, and the hydrogen chloride of excess influences whether follow-up
Rectification.
Notification number is that the patent documentation of CN1041522C discloses a kind of method removing silane containing hydrogen from methylchlorosilane, tool
Body as under conditions of Metal Palladium or platinum catalyst silane containing hydrogen heterogeneous catalytic reaction can be occurred to produce corresponding chlorine silicon with chloro-hydrocarbons etc.
Alkane.The method reaction efficiency is high, is greatly improved the space-time yield of later separation equipment.
The most domestic never breakthrough in terms of separating methylchlorosilane mix monomer, in order to make China's organosilicon technology go up one again
Individual step, the bottleneck problem removing the close impurity of boiling point in dimethyldichlorosilane is urgently to be resolved hurrily.
Summary of the invention
The invention provides the purifying technique of a kind of dimethyldichlorosilane, solve prior art and be difficult to remove and dimethyl dichloro
Ethyl dichloro silane containing hydrogen impurity that silane boiling point is close and cause the problem that its purity is low.
The purifying technique of a kind of dimethyldichlorosilane, comprises the following steps:
(1) by dimethyldichlorosilane crude product by de-low tower, low-boiling-point substance is removed, it is thus achieved that the first intermediate product；
(2) being passed through in de-relative superiority or inferiority tower by the first intermediate product, top gaseous phase is passed through fixed bed reactors after mixing with hydrogen chloride gas,
Under catalyst action, the silane containing hydrogen in crude product is changed into corresponding chlorosilane, it is thus achieved that the second intermediate product；
(3) by the second intermediate product by de-Gao Shangta, the chlorosilane described in removing, it is thus achieved that end product.
Dimethyldichlorosilane crude product of the present invention refers to that direct method produces the dimethyldichlorosilane obtained, owing to technique limits
System, there is also minimal amount of low-boiling-point substance, high-boiling components and ethyl hydrogen dichlorosilane.Dimethyldichlorosilane passes through rectification and purification, pure
Spending the highest, the energy of consumption is the most, and cost is the highest.It is especially when purity is higher than more than 99%, very big by the difficulty of rectification and purification,
And energy resource consumption exponentially increases.The present invention is to be further purified on the basis of the dimethyldichlorosilane through rectification purification,
On the one hand can reduce energy consumption, reduce cost, on the other hand allow its purity reach higher rank.
Low-boiling-point substance of the present invention refers to that boiling point is less than the component of 40 DEG C, and described high-boiling components refers to that boiling point is higher than the component of 70 DEG C.
Described catalyst is carbon supported palladium.The particle diameter 2～3mm of described carbon supported palladium, specific surface is 500～1200m2/g.Described urge
Agent have employed the absorbent charcoal carrier of high-ratio surface, and then the utilization rate of raising noble metal catalyst, concurrently facilitates inactivation catalysis
The recovery of active component in agent.
The preparation method of described catalyst is: carrier carbon immerses palladium source solution a period of time, is subsequently adding precipitant, and it is heavy to collect
Form sediment, with hydrogen as reducing agent, metal ion is reduced into metallic state by ionic state, prepare described catalyst.
Described dimethyldichlorosilane crude product is 200～500:1 with the mass ratio of hydrogen chloride.
The air speed of described fixed bed reactors is than for 7t/m3·h.Fixed bed reactors reaction temperature is 90 DEG C.
For improving the purity of dimethyldichlorosilane further, described product completely or partially returns and is passed through de-with the first intermediate product
Relative superiority or inferiority tower.
The present invention also provides for the purification system of a kind of dimethyldichlorosilane, including:
De-low tower, the charging aperture of the de-relative superiority or inferiority tower of bottom discharging opening connection, for removing the low-boiling-point substance in dimethyldichlorosilane crude product；
De-relative superiority or inferiority tower, the charging aperture of top discharging opening connection fixed bed reactors, for removing in dimethyldichlorosilane crude product
High-boiling components；
Fixed bed reactors, discharging opening connects the charging aperture of de-Gao Shangta, is used for and hcl reaction, by dimethyldichlorosilane
Silane containing hydrogen remaining in crude product changes into corresponding chlorosilane；
De-Gao Shangta, for removing described chlorosilane.
The charging aperture of described de-low tower connects dimethyldichlorosilane crude product storage tank by pipeline, between pipeline be provided with effusion meter
And infusion pump.
The top discharging opening of described de-Gao Shangta connects the charging aperture of de-relative superiority or inferiority tower, and portion of product can be allowed to be back to de-relative superiority or inferiority tower weight
Multiple operation, to improve purity.
The top discharging opening of described de-low tower connects low-boiling-point substance storage tank, and the bottom discharging opening of described de-relative superiority or inferiority tower connects high-boiling components storage tank.
The charging aperture of described fixed bed reactors connects hydrogen chloride storage tank.
Further, the pipeline between hydrogen chloride storage tank and fixed bed reactors is provided with effusion meter.
The beneficial effect that the present invention possesses:
(1) present invention utilizes hcl reaction that silane containing hydrogen is transformed into chlorosilane, it is to avoid hydrogen carry out downstream product add man-hour and its
His group or additive react further and cause properties of product to decline；Ethyl dichlorosilane is transformed into high boiling ethyl trichlorine
Silane, it is simple to separate.
(2) the catalyst Pd/C that prepared by the present invention can effectively be catalyzed the ethyl dichlorosilane chlorination of trace, and catalysis is active and stable
Property is good.
(3) utilize technical scheme, the purity of dimethyldichlorosilane can be allowed to reach more than 99.98%, the removal of impurity
Rate reaches more than 99.9%.
Accompanying drawing explanation
Fig. 1 is the structural representation of purification system of the present invention.
Detailed description of the invention
Below in conjunction with specific embodiment, the invention will be further described, but following embodiment is only the preferred embodiments of the present invention,
And it is not all.Based on the embodiment in embodiment, those skilled in the art are obtained on the premise of not making creative work
Obtain other embodiments, broadly fall into protection scope of the present invention.
As it is shown in figure 1, the purification system of a kind of dimethyldichlorosilane, including de-low tower 1, de-relative superiority or inferiority tower 2, fixed bed reaction
Tower 4 on device 3 and Tuo Gao, the charging aperture of de-low tower 1 connects raw material storage tank 5, between pipeline be provided with effusion meter and delivery pump,
The top discharging opening of de-low tower 1 connects low-boiling-point substance storage tank 7, and bottom discharging opening connects the charging aperture of de-relative superiority or inferiority tower 2.De-relative superiority or inferiority tower 2
Top discharging opening connect the charging aperture of fixed reactor 3, bottom discharging connects high-boiling components storage tank 8, fixed bed reactors 3
Charging aperture is also connected with hydrogen chloride storage tank 6, between pipeline be provided with effusion meter.The discharging opening of fixed bed reactors 3 connects on de-height
The charging aperture of tower 4, the bottom discharging opening of the upper tower 4 of de-height connects ethyl trichlorosilane storage tank 9, and top discharging opening connects de-relative superiority or inferiority
The charging aperture of tower 2 and product reservoir (not shown).
The de-low tower 1 of dimethyldichlorosilane crude product input, low-boiling-point substance is separated, and preserves at low-boiling-point substance storage tank 7 after liquefaction,
Remaining component is admitted to de-relative superiority or inferiority tower 2 again, and high-boiling components is separated, and preserves at high-boiling components storage tank 8, gaseous component and chlorine
Change hydrogen jointly enters fixing fluidized bed reactor 3 and reacts, and ethyl dichlorosilane therein is converted into ethyl trichlorosilane, carries
Boiling-point difference between high dimethyldichlorosilane and impurity composition, product is passed through the upper tower 4 of de-height again, by ethyl trichloro silicane
Alkane is separated off, and is saved in ethyl trichlorosilane storage tank 9, and the gas-phase product purity at top is the highest, as pure in order to improve it
Degree, can return part or all of product, is fed again into de-relative superiority or inferiority tower 2.
Distillation operation of the present invention all uses existing technological parameter, and main contributions of the present invention is, in distillation process, removes height
After boiling thing, gas-phase product is reacted with hydrogen chloride, ethyl dichlorosilane is converted into ethyl trichlorosilane.Because ethyl two
The boiling point of chlorosilane and dimethyldichlorosilane very close to, if utilizing merely rectification remove impurity, energy resource consumption is very big, production cost
The highest, and end product can not reach the highest purity.
Embodiment 1 prepares catalyst Pd/C
1, prepared by catalyst Pd/C
Carbon supports (natural coconut husk processes), respectively through HCl, H2O2、HNO3After carrying out pretreatment, after taking 5g activation
Carrier carbon immerse 50mL containing 0.05gPdCl2Solution in, make Pd be adsorbed in activated carbon duct, utilize NaOH as heavy
Shallow lake agent, collects precipitation, washing, and Pd is reduced into metallic state by ionic state as reducing agent by dried use hydrogen, blunt through nitrogen
Obtaining after change can the finished catalyst of existence stable in the air.Obtain the catalyst Pd/C that Pd load capacity is 1%.
2, catalyst performance detection
Finished catalyst is 500～1200m through surveying specific surface2/g。
The impact on chlorination reaction of the embodiment 2-10 fixed bed reaction condition
The dimethyldichlorosilane crude product of vaporization is (containing EtHSiCl2200ppm) after de-low tower and de-relative superiority or inferiority tower, top gaseous phase with
Hydrogen chloride gas is passed through in fixed bed reactors according to the mass ratio of 500:1, and reaction temperature is respectively 70,90,110 DEG C, air speed
Than respectively 5,7,10t/m3H, by the gas-phase product that exports in fixed bed reactors by tower rectification on de-height, detects product
In EtSiHCl2Content, the results are shown in Table 1.
Table 1
From data above, in fixed bed reactors, reaction temperature is 90 DEG C, and air speed is than for 7t/m3During h, EtSiHCl2With hydrogen chloride
React the most thorough.
The impact on refining effect of the embodiment 11-15 hydrogen chloride intake
The dimethyldichlorosilane crude product of vaporization is (containing EtHSiCl2After 200ppm) by de-low tower and de-relative superiority or inferiority tower, intermediate product
It is passed through in fixed bed reactors according to the mass ratio of 200:1,500:1,1000:1 and 2000:1 respectively with hydrogen chloride gas, reaction
Temperature is 90 DEG C, and air speed is than for 7t/m3H, passes sequentially through the gas-phase product exported in fixed bed reactors temperature and controls at 75 DEG C
De-Gao Shangta, EtSiHCl in the product obtained2Residual quantity, the results are shown in Table 2.
Table 2
Claims (9)
1. a purifying technique for dimethyldichlorosilane, comprises the following steps:
(1) by dimethyldichlorosilane crude product by de-low tower, low-boiling-point substance is removed, it is thus achieved that the first intermediate product；
(2) being passed through in de-relative superiority or inferiority tower by the first intermediate product, top gaseous phase is passed through fixed bed reactors after mixing with hydrogen chloride gas,
Under catalyst action, the silane containing hydrogen in crude product is changed into corresponding chlorosilane, it is thus achieved that the second intermediate product；
(3) by the second intermediate product by de-Gao Shangta, the chlorosilane described in removing, it is thus achieved that product.
2. purifying technique as claimed in claim 1, it is characterised in that described catalyst is carbon supported palladium.
3. purifying technique as claimed in claim 2, it is characterised in that the preparation method of described catalyst is:
Carrier carbon is immersed palladium source solution a period of time, is subsequently adding precipitant, collect precipitation, with hydrogen as reducing agent, by gold
Belong to ion and be reduced into metallic state by ionic state, prepare described catalyst.
4. purifying technique as claimed in claim 1, it is characterised in that described dimethyldichlorosilane crude product and the matter of hydrogen chloride
Amount ratio is 200～500:1.
5. purifying technique as claimed in claim 1, it is characterised in that the air speed of described fixed bed reactors ratio is for 7t/m3H,
Reaction temperature is 90 DEG C.
6. purifying technique as claimed in claim 1, it is characterised in that described product completely or partially returns and produces in the middle of first
Thing is passed through de-relative superiority or inferiority tower.
7. a purification system for dimethyldichlorosilane, including:
De-low tower, the charging aperture of the de-relative superiority or inferiority tower of bottom discharging opening connection, for removing the low-boiling-point substance in dimethyldichlorosilane crude product；
De-relative superiority or inferiority tower, the charging aperture of top discharging opening connection fixed bed reactors, for removing in dimethyldichlorosilane crude product
High-boiling components；
Fixed bed reactors, discharging opening connects the charging aperture of de-Gao Shangta, is used for and hcl reaction, by dimethyldichlorosilane
Silane containing hydrogen remaining in crude product changes into corresponding chlorosilane；
De-Gao Shangta, for removing described chlorosilane.
8. purification system as claimed in claim 7, it is characterised in that the charging aperture of described de-low tower connects diformazan by pipeline
Base dichlorosilane crude product storage tank, between pipeline be provided with effusion meter and infusion pump.
9. purification system as claimed in claim 7, it is characterised in that the top discharging opening of described de-Gao Shangta connects de-relative superiority or inferiority
The charging aperture of tower.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610301102.6A CN105906659B (en) | 2016-05-06 | 2016-05-06 | A kind of purifying technique and system of dimethyldichlorosilane |
Applications Claiming Priority (1)
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| CN109731364A (en) * | 2018-12-14 | 2019-05-10 | 浙江开化合成材料有限公司 | A kind of high water-saving rectification and hydrolization technology system of methyl chlorosilane monomer |
| CN110639221A (en) * | 2019-10-15 | 2020-01-03 | 天津大学 | Method and device for purifying dimethyldichlorosilane by reactive distillation and impurity removal |
| CN113845542A (en) * | 2021-10-29 | 2021-12-28 | 新疆晶硕新材料有限公司 | Method and system for removing ethyl hydride in crude dimethyldichlorosilane |
| CN113893850A (en) * | 2021-10-27 | 2022-01-07 | 北京国化新材料技术中心(有限合伙) | Catalyst for purifying dimethyldichlorosilane and preparation method and application thereof |
| CN114853801A (en) * | 2022-04-29 | 2022-08-05 | 湖北兴瑞硅材料有限公司 | Process for removing impurities in organic silicon monomer rectification process |
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| CN109731364A (en) * | 2018-12-14 | 2019-05-10 | 浙江开化合成材料有限公司 | A kind of high water-saving rectification and hydrolization technology system of methyl chlorosilane monomer |
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| CN114853801A (en) * | 2022-04-29 | 2022-08-05 | 湖北兴瑞硅材料有限公司 | Process for removing impurities in organic silicon monomer rectification process |
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